1. Field of the Invention
The present invention relates to novel polycationic block copolymers of use inter alia as antistatic aids in detergent formulations and as flocculating agents.
2. Prior Art
Polymeric quaternary ammonium compounds have been known for many years. For example U.S. Pat. No. 2,261,002 describes such compounds as having use as photographic chemicals, pesticides, pour point depressants, pigment dispersion control agents and surface active agents.
U.S. Pat. No. 3,632,559 (Matter, issued Jan. 4, 1972) describes cationically active water soluble polyamides obtained by alkylation of a polyamide with a bifunctional alkylation agent.
U.S. Pat. No. 4,166,894 (Schaper Sept. 4, 1979) describes functional ionene polymer compositions of use as wet and dry strength additives, corrosion inhibitors and electroconductive coatings.
U.S. Pat. No. 3,734,889 of Lipowski et al describes the production of quaternary aminoplast polymers by reaction of for example dimethylamino propylamine with adipic acid followed by chain extension with for example dichloroethyl ether. Most of the products obtained are of relatively low molecular weight although reference is made to products containing up to b 1,000 repeating units. The products are not block copolymers and are useful as flocculants, drainage aids and as dry strength resins in paper manufacture. U.S. Pat. No. 4,505,833 of Mar. 19, 1985 also to Lipowski et al describes the use of such products to prevent, inhibit or reduce swelling or migrating of clay particles in a clayey geological formation.
British Patent Application No. 2,066,663 A in the name of L'Oreal (apparently equivalent to U.S. Pat. No. 4,517,174 of May 14, 1985) describes a wide variety of quaternary polymers of use in cosmetics. Included among the products of that invention are in Example 45 condensation copolymers containing alternating units derived from a ditertary amine and a dihalide of the formula: ##STR3##
So far as applicants are aware, however, there has been no previous suggestion of the utility of polycationic block copolymers wherein the blocks are of different types of monomer units.
U.S. Pat. No. 4,157,388 of Christiansen describes compositions containing polyquaternary ammonium compounds for use as hair conditioners and antistats and humectants for fibrous textile products. The products are polymers formed by quaternizing the product of a reaction between tertiary amines and urea with a dihalide. If desired one can link blocks of units of the products obtained using one particular amine to blocks wherein a different amine is employed. These compounds are generally liquid at room temperature. Mirapol.RTM. A-15 is a compound in accordance with Examples of Christiansen having the formula: ##STR4## wherein n is at least one.
In commonly assigned copending application Ser. No. 758483 filed on July 24, 1985 which is a continuation in part of application Ser. No. 485197 filed on Apr. 15, 1983, now abandoned, there are described products of the general Formula: ##STR5## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 may be the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, propyl, --CH.sub.2 CH.sub.2 OH, --CH.sub.2 CH(OH)CH.sub.3 and --CH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2).sub.p OH wherein p is an integer from 0 to 6 with the proviso that not all of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are hydrogen;
x and y are the same or different and are an integer from 1 to 6; PA1 n is a value such that the number average molecular weight of the product is in excess of 20,000; PA1 m is an integer from 0 to 34, for example 3-10, typically 4-7; PA1 X is halogen; PA1 Z is halogen or amino-diamido ammonium residue; and PA1 A is the residue of a dihalide. PA1 A is ##STR6## wherein: R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8 may be the same or different and are generally selected from the group consisting of C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 hydroxyalkyl, or hydroxy polyalkylene; PA1 p, q, r and s are the same or different and are an integer from 1 to 6 and m is an integer from 0 to 34; PA1 D is a halide ion; PA1 L is a linkage derived from a dihalide, x and y are integers ranging from 1-100 and Q is (BL).sub.y where the bonds between L and A or B are carbon-nitrogen bonds formed by quaternization of the tertiary amine functions of A and B by the organic dihalides from which L is derived and W is 0 or 1; which are obtained by first forming a block of units by reacting a monomer of the formula II ##STR7## wherein each of R.sub.5, R.sub.6, R.sub.7 and R.sub.8 may be the same or different and is selected from the group consisting of C.sub.1-3 alkyl, C.sub.1-3 hydroxy alkyl and hyroxy polyalkylene, PA1 m is an integer from 0 to 34 and PA1 r and s are the same or different and are integers from 1 to 6, PA1 with a molar excess of a dihalide of the formula EQU Hal--L--Hal PA1 wherein Hal represents a halogen atom and L is selected from --CH.sub.2 CH.sub.2 --O--CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 --O--CH.sub.2 CH.sub.2 --O--CH.sub.2 CH.sub.2 --, --(CH.sub.2).sub.t -- and --CH.sub.2 CHOHCH.sub.2 -- where t is an integer from 2 to 6 and thereafter reacting the product so formed with a compound of the formula III ##STR8## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each individually selected from the group consisting of C.sub.1-3 alkyl, C.sub.1-3 hydroxyalkyl and hydroxy polyalkylene and p, and q are each individually integers of from 1 to 6 and, if necessary, in order to ensure a total molar ratio of compounds of Formulae II and III to those of the formula Hal--L--Hal of 1:1, reacting the product with further compound of the formula Hal--L--Hal. PA1 R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are preferably each individually alkyl and are typically methyl or ethyl, PA1 p, q, r and s are each typically 2, 3 or 4; PA1 m is preferably 3-10, typically 4-7.